Transformation of isatin with P4S10 to pentathiepino[6,7-b]indole in one step

Bergman, Jan; St»lhandske, Claes

doi:10.1016/s0040-4039(00)77084-5

Cited by 35 publications

(21 citation statements)

References 19 publications

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“…The crystal structure of pentathiepino(6,7-b)indole (13) represents an unusual case where a secondary amine is fused in a 1,3-position relative to sulfur S1 (Scheme 3). 26 Since little is known of the role of amine in pentathiepin natural products, we thought the research should focus on unimolecular reactions of the marine toxins 1 and 2 and a series of pentathiepin derivatives (14-20, Scheme 3). The computations and experiments provide the first evidence that nucleophilic attack of amine on S1 sulfur underpins the production of reactive sulfur intermediates, and provides mechanistic insight into the process that gives rise to biological activity.…”

Section: Resultsmentioning

confidence: 99%

The Role of Amine in the Mechanism of Pentathiepin (Polysulfur) Antitumor Agents

Brzostowska

Greer

2002

J. Am. Chem. Soc.

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A computational and experimental study is presented, which provides the first evidence that amine has an opportunity to engage in bonding with pentathiepin to promote its decomposition. The study provides mechanistic insight into the process that gives rise to pentathiepin biological activity. Primary or secondary amine will allow for an intramolecular addition to the pentathiepin ring at the nearest sulfur (S1). In contrast, tertiary amine adds reversibly to S1, because nitrogen cannot lose its positive charge by deprotonation. This precludes the amine promotion step. An energetically low-lying process is characterized, corresponding to S3-loss triggered by nucleophilic activation with a primary or secondary amine. Pentathiepin desulfurization via S3-unit transfer is supported by a trapping study with norbornene. That the amine may confer an enhanced reactivity in the natural products varacin, 1, and lissoclinotoxin A, 2, adds to the understanding of the pathway for pentathiepin activation and may provide new design concepts that have potential applications for this class of biocides.

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Section: Resultsmentioning

confidence: 99%

The Role of Amine in the Mechanism of Pentathiepin (Polysulfur) Antitumor Agents

Brzostowska

Greer

2002

J. Am. Chem. Soc.

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“…The structure was assigned on the basis of NMR, IR and MS data, and was further supported by elemental analysis as well as UV-VIS measurements. Monothioindigo (6) displayed a visible light absorption maximum in ethanol at λ max = 582 nm, comparable with indigo (7), which exhibits a λ max at 610 nm. 8 The isolation of 6 constitutes the first example of a thionated indigo derivative with an established structure.…”

Section: Resultsmentioning

confidence: 99%

“…Previously, we have reported the isolation of pentathiepino-[6,7-b]indole (4) from the treatment of isatin † (5) with P 4 S 10 in refluxing pyridine. 7 This reaction also gives rise to two other isolable products which can be separated using chromatography on silica gel. A deep blue compound assigned the structure 6 (i.e.…”

Section: Resultsmentioning

confidence: 99%

Thionation of bisindole derivatives with P4S10 or elemental sulfur

Janosik

Bergman

Stensland

et al. 2002

J. Chem. Soc., Perkin Trans. 1

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“…The synthesis and reactivity of compounds containing multi-sulfur linkage have been studied extensively [ 11 , 12 , 13 , 14 , 15 , 16 , 17 ]. Many methods have been developed to prepare cyclic polysulfides by using either elemental sulfur or other sulfur-transfer reagents, however, these methods often gave poor yields of the desired products and require extreme precaution [ 18 , 19 , 20 ]. There are few samples for the synthesis of the sulfur-phosphorus compounds with O-(P)-S-S-(P)-O scaffold.…”

Section: Introductionmentioning

confidence: 99%

Phosphorus-Sulfur Heterocycles Incorporating an O-P(S)-O or O-P(S)-S-S-P(S)-O Scaffold: One-Pot Synthesis and Crystal Structure Study

et al. 2017

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A new one-pot preparative route was developed to synthesize novel organophosphorus-sulfur heterocycles via the reaction of the four-membered ring thionation reagent [2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide (FcLR, a ferrocene analogue of Lawesson’s reagent)] and alkenyl/aryl-diols and I2 (or SOCl2) in the presence of triethylamine. Therefore, a series of five- to ten-membered heterocycles bearing an O-P(S)-O or an O-P(S)-S-S-P(S)-O linkage were synthesized. The synthesis features a novel application of the multicomponent reaction, providing an efficient and environmentally benign method for the preparation of the unusual phosphorus-sulfur heterocycles. Seven representative X-ray structures confirm the formation of these heterocycles.

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Transformation of isatin with P4S10 to pentathiepino[6,7-b]indole in one step

Cited by 35 publications

References 19 publications

The Role of Amine in the Mechanism of Pentathiepin (Polysulfur) Antitumor Agents

The Role of Amine in the Mechanism of Pentathiepin (Polysulfur) Antitumor Agents

Thionation of bisindole derivatives with P4S10 or elemental sulfur

Phosphorus-Sulfur Heterocycles Incorporating an O-P(S)-O or O-P(S)-S-S-P(S)-O Scaffold: One-Pot Synthesis and Crystal Structure Study

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